Organic materials with linearly polarized luminescence (LPL) properties and good processability are critical to the development of advanced optical devices. To fabricate polymer-stabilized thin films with LPL properties, dicyanodistyrylbenzene-based reactive luminogens (abbreviated as DRL) containing both vinyl and thiol units were newly synthesized. On the basis of morphological observations combined with thermal and scattering analyses, it was found that DRL has a nematic liquid crystal mesophase. DRL molecules were uniaxially oriented by surface alignment layer and stabilized by thiol-ene click reaction. Uniaxially oriented and polymer-stabilized DRL thin films showed excellent chemical resistance as well as mechanical and thermal stability due to the chemically cross-linked polymer network. The DRL polymer film exhibited strong emission at 564 nm with remarkable LPL property. The polymer-stabilized films obtained from reactive luminogens with aggregation-induced enhanced emission (AIEE) properties have great potential for the application of advanced optical devices.